JPS5814943A - Photocurable microcapsules - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photocurable@-1 microcapsules with controllable destruction.

Microcapsules encapsulate minute particles'?, liquids, solids, and gases with a size of 1 μm to several hundred x mt''e, and uniformly cover them with a thin film of several micrometers to several hundred meters. 4
0”5AJ), U.S. EiO Patent No. 2711376, No. 2
Since it was disclosed in the specification of No. 12607, it has come to be used for various purposes.

The most common application is to pressure-sensitive recording paper, in which microscopic paper is coated with an oil containing a coloring agent, which is a colorless electron-donating dye precursor, dissolved in a non-volatile solvent on the back side of the support. Microcapsules are formed by stacking the upper paper coated with capsules and the lower paper coated with a color developer so that their coated surfaces face each other and applying linear pressure to the surface of another support. is destroyed, the inclusions are released, and the color forming agent and color developer come into contact and a chemical reaction forms a colored substance on the surface of the lower paper, which is what is obtained as a copy image.

In this way, microcapsules form a film on the outside of a substance that has certain properties, and can simultaneously confine those properties.

When necessary, the substance can be extracted by destroying K111K. O-1' allows substances that easily react with each other to be isolated by microcassellation.

Even after mixing for a long time, no reaction was observed at t9, and it is possible that the reaction starts only when the microcapsules are destroyed. Wear. Utilizing these functions of microcapsules, it can be used for recording materials, W1 drugs, food, cosmetics, etc.
It has come to be used for adhesives, pesticides, artificial organs, etc., and floor desks.

In addition, the degree of formation and degree of crosslinking of microcapsules, t
Microcapsules that gradually release their contents by changing their permeability! By changing the size and film thickness of the liquid, it is possible to produce microcapsules that are difficult to break even when a strong force is applied, while microcapsules are easily broken even with a weak force. And the means to destroy the capsule is not just pressure, but heat.

A song that helps you think about light, electric current, and sH.

U.S. Patent No. 5212896, 41st Edition 1844-2
No. 6579, No. 49-265G) No. 7, JP-A-62-!
- Publication No. 1451046 etc. discloses that heating causes the membrane of the microcapsule to rupture and melt, releasing the contents;
4! JP-A-54-10G1078 Bulletin Ka, irradiating the microphone with light will cause the O membrane of the microphone capsule to deteriorate and release the inclusions, and JP-A-54-GI9969 reports that the microphone capsule is brought into contact with water. Humans have been disclosed that destroy the membrane and release the inclusions.They all have 4I characteristics on the membrane of the microcapsules, and the inclusions of the microcapsules have been released. Development is progressing on how to release it. However, in such microcapsules, when the inclusions are unnecessary and the microcapsules do not want to be destroyed, -
Microcapsules have been created to allow you to freely control the destruction of the microphone capsule as needed, such as when you want to release only the contents of the microcapsule. After that, the INK is kept in a state of constant destruction.

The inventors of the present invention conducted 99 rounds of research to obtain microcapsules whose destruction can be controlled, and as a result, by encapsulating a photocurable resin and a photopolymerization initiator in microcapsules, microcapsules whose destruction can be freely controlled are created. I found out.

Photo-cured soda microcapsules, which mainly contain photo-cured resin and photopolymerization initiator, are used to control the destruction of microcapsules using light.
As with normal microcapsules, by applying pressure, heat, humidity, etc. from the outside, the membrane can be destroyed and the contents can be released. It was. When you want to keep the contents inside the capsule! When light is applied to the cap, the light passes through the membrane and damages the inclusions, hardens the light-curing lid resin and changes it into a hard resin. As a result, the photo-curable microcapsules are no longer destroyed by external force, and the release of the inclusions does not occur. Material O release S*
You can also control the real 110 light curing! 1. Microcapsules must contain Dukorei resin and photopolymerization initiator.
It is also possible to encapsulate any other substance. Not specified in particular, but pesticides.

Foods, cosmetics, catalysts, adhesives, curing agents, oxidizing agents, reducing agents, dyes, pigments, plating agents, polymer flocculants.

Organic substances, inorganic substances, etc. can be incorporated into the inclusions in a solid or liquid state because they are used as rust-spinning agents, antioxidants, soil conditioners, etc. The photocurable W microcapsules of the present invention can be used in cans. For example, light curing can be used for floor desks in the field. ! I! A reactive substance is added to some of the inclusions of Iku Shikashiryu, and when the #capsules are coated on a support and exposed to light, the degree of hardening of the capsules varies depending on the amount of exposure.The amount of inclusions released Different microcapsules are produced. An optical sensor that displays the amount of exposure in terms of color shading by stacking it on a support coated with a co-reactive substance that reacts with the reactive substance to form a colored substance and pressurizing it with a constant pressure. Also, when a support coated with photocurable microcapsules to which a reactive substance is added is overlapped with an original and exposed, the imaged area of the original does not pass or reflect light, so the capsules remain in their ★t state. Although the capsule is sagging, the rest of the capsule is rounded when exposed to light and hardens from the inside. Then, when pressed together with the image-receiving sheet coated with a co-reactive substance, the image-receiving sheet K
It is possible to obtain a copy of M manuscripts, and it is also possible to make multiple copies.It can also be used as a table copy material, but is not limited to these.
Any material that can utilize the functions of photocurable deaf microcapsules can be used freely.

The photocurable resin encapsulated in the photocurable microcapsules used in the present invention includes cinnamic acid residues, yyt<vden residues, α,! - Photodimerizable resin with photosensitive group of unsaturated ketone residue, anthracene residue, α-7 winged diruyl tr residue, -4 nzoff winged non-residue, stilbene residue, diazonium salt residue 4 photosensitive groups such as quinone diazi-P residue, adi-P residue, dithiocar Amate residue, and -1-inzoin residue; photodegradable resin; A photopolymerizable resin or the like can be optionally used. In particular, a liquid photopolymerizable resin is advantageously used as an effective form of the photopolymerizable resin. Also.

As a photopolymerization initiator for superimposing the photocurable lid resin, 1. Commonly used O-compounds such as pyzoin alkyl ether, benzo 7-chloride, and Michler's ketone 1 can be used.
Thioxatones, acetophones, etc. are used as photosensitizing aids that have the effect of broadening the sensitizing wavelength range of the photopolymerization initiator, such as ant-2, 5-Ja)-fluorene, etc. In order to improve storage stability, a diluent such as a polymerization inhibitor, a stabilizer, a modifier, and a relatively low molecular weight oligomer monomer may be included at the same time. At the same time, in order to improve the solubility of the substance to be encapsulated, oil-based solvents with high boiling points, such as alkylnaphthalates, alkylpiphenyls, alkyritene-phenyls, esters, etc., are sometimes used as dissolution aids. It is inappropriate to use a large amount of rounding, which adversely affects the degree of hardening.

Ultraviolet light is generally used as the light for curing the photocurable gourd capsules used in Honji 1jiK.The light source is:
Sunlight, xeno/lights, low-pressure and high-pressure mercury lamps, warning lights, etc. are used. The deterioration of exposure 1 during manufacturing and normal handling time of light-curing type Kazoce Pyolli Injection, which occurs with Tominai lamps and sunlight outside the company, is rarely seen.

The microphone capsule used in the present invention can be manufactured by methods well known in the art. For example, the phase separation method from an aqueous solution as shown in U.S. Patent No. 2800457, U.S. Patent No. 2800 δ6, etc., Japanese Patent Publication No. 1!131
Interfacial polymerization methods as shown in Publication No. 3-1957-4, Publication No. 46 of 1971, Publication No. 771 of 1971, etc.
Special meeting 1968-91681) Newsletter, q# Kaisho 5l-107
In-company t due to heavy inclusion of peaks shown in G1 publication etc.
u law, UK 11411 Permit No. G15280T, same No. 965
The methods are limited to the melting and dispersion cooling method shown in the US Patent No. 5111 No. 07, the spray r-line I method shown in the British Patent No. 93-0422, etc. It's not a thing.

The bottled wall film-forming materials include gelatin, a2t arm, defsin, sodium aluminate/ethylcellulose, caloxymethylcellulose 1$-lime alcohol, df9
Ethylene, /riaP.

-Reester, Bori urethane, Iriechirei #yll
However, when manufacturing a photocurable microcrystalline resin, it is more preferable to select a material that can sufficiently transmit light, especially ultraviolet light.

The present invention will be specifically explained below with reference to Examples. Note that "parts" indicate parts by weight.

Example 1 Photo-curing! ! ! Iku4 capsule dispersion was prepared as follows.9.

Styrene - Anhydrous! Into 100 parts of -4005- aqueous solution in which leic acid copolymer was dissolved together with a small amount of sodium hydroxide, 780 parts of engineering S + diacrylate-based hardened resin (trade name Ri4meishi, Showa Kobunshi ■11) and -4y were added. A mixture of 2 parts of zoin ethyl ether α was emulsified, while Meladen ylo part, 3711 formaldehyde aqueous solution 26 parts, water 65
111 (9) with sodium hydroxide 7 oxide and heated to 60°C. After 16 minutes, a transparent and formalized/initial condensate was obtained. Add the initial condensate of H to the above emulsion. After the addition, the liquid temperature was raised to 60°C, stirring was continued for 4 hours, and then the mixture was cooled to room temperature.

10 parts to 50 parts of the obtained photocurable microphone four capsule dispersion.
1G/S C Nyl Alcohol Aqueous Solution 2011 Add 40 parts of water, stir thoroughly, and then mix with Mayer/e- to give a basis weight of 50 gA.
Apply it evenly to the paper in I and let it dry.

Spread black paper on a part of the coating surface of this photocurable microcapsule sheet, and use Siliso Xenofax FX to avoid the trouble of coating.
-1δO was used to expose 51!1 xenon light and mourn. After removing the black paper and applying pressure to the entire surface of the pressure roll f, the exposed and unexposed areas were observed under an electron microscope, and the microcapsules in the exposed areas were not destroyed and maintained their spherical shape.

It was confirmed that all the microcapsules in the unexposed area were destroyed.

Example 2 Instead of the mixture of Nyxacrylate photocurable resin waO part and 0.2 part of benzoin ethyl ether in Example 1, an olino ester acrylate photocurable resin (trade name: Aronix was manufactured by Toagosei Kagaku Kogyo Co., Ltd.) ■) 80 copies, 3-
A photocurable i-icrocapsule dispersion was prepared in the same manner except that a mixed solution of 3 parts of diethyl adeno7'' chlora fluorane and 0.2 parts of -4-ion ethyl ether was used. To 50 parts of the dispersion, 20 parts of a 10$df9♂Glualp1 aqueous solution and 40 parts of water were added, thoroughly stirred, and then coated uniformly on paper with a basis weight of 100 kg using a Mayer/Say machine and dried. Litho-Xenofax F! is applied to the coated surface of this photocurable microcapsule sheet. -1δO was used to emit xenon light from 1 to 5 times at f'4. 3.5-G tart-
When a mixed dispersion of decyl isthyl acid and zinc oxide was applied, the image-receiving sheet and the coated surface were stacked so that they faced each other, and the entire surface was pressurized with a pressure roll, 7 impressions appeared on the image-receiving sheet, so the number of exposures was Red color images with different densities were obtained.

Table 1 shows the relationship between the number of exposures and the red density of the red color image obtained on the damaged sheet. A high-density color image can be obtained on the rolled image-receiving sheet, but by increasing the number of exposures, the miter fog will harden and be destroyed! The number of Ikushikazoryuuru is decreasing. For this reason, the color density decreases by 9 IP in the number of exposures,
Eventually, when the microcapsules completely harden and become rigid cassicles, the microcapsules will no longer be destroyed. Therefore, it can be seen that no color develops on the image-receiving sheet.

Claims (1)

[Claims] 1. Photocurable microcapsules that mainly contain a photocurable resin and a photopolymerization initiator.